EP2493903A1 - Verfahren zur herstellung von konjugierten dienphosphonatverbindungen - Google Patents

Verfahren zur herstellung von konjugierten dienphosphonatverbindungen

Info

Publication number
EP2493903A1
EP2493903A1 EP09850739A EP09850739A EP2493903A1 EP 2493903 A1 EP2493903 A1 EP 2493903A1 EP 09850739 A EP09850739 A EP 09850739A EP 09850739 A EP09850739 A EP 09850739A EP 2493903 A1 EP2493903 A1 EP 2493903A1
Authority
EP
European Patent Office
Prior art keywords
carbon atoms
cycloalkyl
conjugated diene
represent
heterocycloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09850739A
Other languages
English (en)
French (fr)
Other versions
EP2493903A4 (de
Inventor
Zhaoqing Liu
Floryan De Campo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay China Co Ltd
Original Assignee
Rhodia China Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia China Co Ltd filed Critical Rhodia China Co Ltd
Publication of EP2493903A1 publication Critical patent/EP2493903A1/de
Publication of EP2493903A4 publication Critical patent/EP2493903A4/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3826—Acyclic unsaturated acids

Definitions

  • This invention relates to a method for preparing conjugated diene phosphonate compounds, especially relates to a method for preparing phosphonated monomer with higher reactivity.
  • Vinyl monomers containing phosphonic acid groups have various applications in industry, for example, their polymer and co-polymers are used as corrosion inhibitor in cooling or boiler water system (US 4,446,046 and 4,201,669); as dispersants in water treatment and pigment dispersion.
  • vinyl monomers such as 1-phenylvinyl phosphonic acid (US 5391,816), vinyl phosphonic acid (US 6,479,687, 5,811,575), acrylamidomethylpropanephosphonic acid (US 4,526,788), isopropenyl phosphonic acid (US4,446,046), chloride substituted phenylvinyl phosphonic acid (US 4,507,249) and diene type of phosphonic acid monomer (US 4,507,249).
  • 1-phenylvinyl phosphonic acid US 5391,816)
  • vinyl phosphonic acid US 6,479,687, 5,811,575
  • acrylamidomethylpropanephosphonic acid US 4,526,788
  • isopropenyl phosphonic acid US4,446,046)
  • chloride substituted phenylvinyl phosphonic acid US 4,507,249
  • diene type of phosphonic acid monomer US 4,507,249
  • Recent US 7,420,081 and 7,442,831 patents described a new way to prepare some of the above monomers from ketone or aldehyde with phosphorous acid in a mixture of acetic acid and acetic anhydride. These monomers include alkyl and aryl substituted vinyl phosphonic acids of lower reactivity toward polymerization. It is still desirable to have an economic process to produce more reactive phosphonic acid-containing monomers.
  • this invention relates to a method for preparing conjugated diene phosphonate compounds with high reactivity, which comprises the step of reacting ⁇ , ⁇ - or ⁇ , ⁇ -unsaturated ketones or aldehydes having the formula I or II, with phosphorous acid or its derivatives optionally in a mixture of acetic anhydride and/or acetic ac
  • the method of the present invention can be used to prepare a variety of phosphonate-bearing conjugated dienes. Some of those dienes will become reactive monomers to make performance polymers and co-polymers. These polymers could find applications in water treatment, oilfield applications, surface treatment applications, mining, dental application, plastics, etc.
  • the monomers prepared according to the present invention alone could be used for the previous applications and provide the advantage that they could be polymerized at surfaces much easier than current commercial monomers.
  • the present invention provides a method for preparing conjugated diene phosphonate compounds from ⁇ , ⁇ - or ⁇ , ⁇ -unsaturated ketones or aldehydes, which comprises reacting an ⁇ , ⁇ - or ⁇ , ⁇ -unsaturated ketone or aldehyde having the formula I or
  • Ri, R 2 , R 3 , R4, and R5 represent, independently, hydrogen, alkyl, aryl, alkaryl, aralkyl, cycloalkyl, heterocycloalkyl, or alkenyl groups; preferably, the said alkyl and alkenyl comprise from 1-24 carbon atoms, said aryl comprises from 6-24 carbon atoms, said alkaryl, aralkyl comprise from 7-24 carbon atoms, and said cycloalkyl, heterocycloalkyl comprise from 3-24 carbon atoms; more preferably, the said alkyl and alkenyl comprise from 1-18 carbon atoms, said aryl comprises from 6-18 carbon atoms, said alkaryl, aralkyl comprise from 7-18 carbon atoms, and said cycloalkyl, heterocycloalkyl comprise from 3-18 carbon atoms.
  • Ri and/or R 2 represent hydrogen, so the monomers so obtained are more reactive toward polymerization.
  • Ri, R 2 and R4 represent hydrogen; or preferably, R 3 and R5 represent methyl. More preferably, Ri, R 2 , and R4 represent hydrogen and R 3 , R5 represent methyl.
  • R6 and R 7 represent, independently, hydrogen, alkyl, aryl, alkaryl, aralkyl, cycloalkyl, alkenyl groups, or metals selected from the group consisting of Na, Li, Ca.
  • the said alkyl and alkenyl comprise from 1-24 carbon atoms
  • said aryl comprises from 6-24 carbon atoms
  • said alkaryl, aralkyl comprise from 7-24 carbon atoms
  • said cycloalkyl, heterocycloalkyl comprise from 3-24 carbon atoms
  • the said alkyl, alkenyl comprise from 1-18 carbon atoms
  • said aryl comprises from 6-18 carbon atoms
  • said alkaryl, aralkyl comprise from 7-18 carbon atoms
  • said cycloalkyl, heterocycloalkyl comprise from 3-18 carbon atoms.
  • R6, and R 7 represent hydrogen.
  • any two of Ri, R 2 , R 3 , R4 and R5 are together formed into a cycloalkyl, or heterocycloalkyl group, which is preferably selected from 5, 6, 7 and 8 membered rings.
  • R 6 and R 7 are together formed into a cycloalkyl, or heterocycloalkyl group, which is preferably selected from 5, 6, 7 and 8 membered rings.
  • the compounds of the present invention may contain one or more chiral centers and/or double bonds and therefore may exist as stereoisomers, such as Z- and E- or cis- and trans-isomers from cyclic structures or double bonds (i.e., geometric isomers), rotamers, enantiomers or diastereomers. Accordingly, when stereochemistry at chiral centers is not specified, the chemical structures depicted herein encompass all possible configurations at those chiral centers including the stereoisomerically pure form (e.g.
  • said compound I or II is added in the molar ratio of (1-1.5) ' . 1 relative to said phosphorous acid or its derivatives; or preferably (1-1.2) ' . 1 relative to said phosphorous acid or its derivatives.
  • the reaction time remains 4-24 hours, or preferably 4-8 hours.
  • the reaction temperature remains at 0-100 ° C , or preferably 20-60 ° C .
  • the reaction according to the present invention may be optionally carried out under protection of inert gas protection.
  • Said inert gas may be selected from, for example, one or more of the group consisting of nitrogen, argon, and carbon dioxide.
  • the preparation method of the present invention is valid whether starting from ⁇ , ⁇ -unsaturated carbonyl compounds or ⁇ , ⁇ -unsaturated carbonyl compounds and both species will lead to the formation of the same diene.
  • mesityl oxide was reacted with phosphorous acid in the presence of acetic anhydride and acetic acid under mild conditions to yield 4-methylpenta-2,4-diene-2-phosphonic acid in more than 90% mole purity.
  • the unsaturated ketones and aldehydes can be obtained from aldol condensations of carbonyl compounds.
  • MIBK methyl isobutyl ketone
  • ketones and aldehydes are important industrial chemicals. They are used as solvents, for example, mesityl oxide, as precursor to other commodity and specialty chemicals, for example, isophorone and as monomer for polymeric materials, for example, methyl vinyl ketone (MVK).
  • solvents for example, mesityl oxide
  • isophorone as precursor to other commodity and specialty chemicals, for example, isophorone and as monomer for polymeric materials, for example, methyl vinyl ketone (MVK).
  • MVK methyl vinyl ketone
  • 3-Methylcrotonaldehyde is a precursor for Vitamine A. Industrially, it is produced from isobutene and formaldehyde:
  • the most attractive one may be crotonaldehyde. It is a biogenic compound, used as florvoring agent. It can be produced from renewable resources of bioethanol:
  • Natural unsaturated ketones and aldehydes can also be used to carry out the reaction. Those include, for example, piperitone, carvone, umbellulone, menthene-2-one, menthene-3-one, verbenone and myrtenal.
  • the resulting phosphonate dienes could be of important biological activities, thus as insecticides, pesticides, pharmaceuticals and their intermediates.
  • the phosphonate diene prepared according to the method of the present invention can be used for making polymers or co-polymers, hi this aspect the invention also relates to a polymer or co-polymer of said conjugated diene phosphonate compounds.
  • the invention also relates to a method for preparing polymers or co-polymers of the phosphonate diene, comprising a step of preparing a phosphonate diene according to the method of the present invention and a polymerization or co-polymerization step.
  • the phosphonate diene prepared according to the method of the present invention, or the polymer or co-polymer can be used as flame retardants, as intermediates for active pharmaceuticals and agrochemicals, as reactive or functional monomers, typically for functional polymers, such as phosphonate-containing polystyrene, polyethylene, polypropylene, poly(meth)acrylates, poly(meth)acrylamide, polybutadiene, polyacrylonitrile, etc. and their copolymers, or building blocks for other useful products.
  • functional polymers such as phosphonate-containing polystyrene, polyethylene, polypropylene, poly(meth)acrylates, poly(meth)acrylamide, polybutadiene, polyacrylonitrile, etc. and their copolymers, or building blocks for other useful products.
  • the phosphonate diene prepared according to the method of the present invention, or the polymer or co-polymer can be used in water treatment applications, in oilfield applications, in surface treatment applications, in mining applications, in dental applications, in plastics, and etc...
  • the phosphonate diene prepared according to the method of the present invention, or the polymer or co-polymer can be used as flame retardants in plastics or textile.
  • the invention also relates to methods comprising these uses.
  • Phosphonate functionalities are well known to provide flame retardant (FR) properties but their synthesis is often difficult and expensive.
  • the process according to the present invention allows a direct access to phosphonate moieties from inexpensive raw materials.
  • the products obtained can also be further reacted to prepare some polymers.
  • the monomers and/or the polymers should provide some significant flame retardant properties if incorporated to plastics, textiles or any other materials.
  • the conjugated dienes prepared according to the process of the present invention may be active or intermediates for pharmaceuticals or/and agroculture chemicals.
  • Phosphonate compounds are well known to have unique properties and are widely used in the pharmaceutical industry. The compounds described here would provide new and unique entitis that could be used to design new drugs. These compounds could also find some use in agriculture.
  • Phosphonate monomers are scarce and typically difficult and expensive to prepare. Also, most of them have a limited reactivity which makes them difficult to use as functional monomers to combine them with other monomers (styrene, ethylene, butadiene, acrylic acid etc .). Incorporating phosphonate moieties into polymers can provide unique properties to the resulting materials such as better mechanical properties, flame reardant properties, sequestration properties, anti-bacterial properties etc. the diene monomer can also be grafted onto synthetic or natural occurring polymers.
  • the present invention also provides polymers prepared from conjugated diene phosphonate compounds of the formula III according to the present invention.
  • R 7 can be H.
  • the invention provides a process to make 1,3-diene phosphonate in one step under mild conditions and using readily available and affordable raw materials. This process is a significant improvement in term of ease of process and cost.
  • the 1,3-diene phosphonate prepared according the present invention allows to develop some original polymers and composition that were not accessible before.
  • the technical solution of the present invention is kind to the environment. Using sustainable and natural raw materials is critical today and many unsaturated ketones or aldehydes are actually natural products.
  • H 3 PO 3 was dried for about 4 hrs at 50 ° C under vacuum. lOg of dried H 3 PO 3 and 12.43 g of mesityl oxide were mixed in a flask at 28-30 ° C . Then 24.7 g of acetic anhydride was added slowly with mixing over 50 mins while the reaction temperature was kept below 30 ° C . The mixture was kept stirring at this temp for 4 hrs. 31 P NMR showed 81.2% conversion of H 3 PO 3 and 86% selectivity for PoDM and its anhydride derivatives.
  • H 3 PO 3 was dried for about 4 hrs at 50 ° C under vacuum. lOg of dried H 3 PO 3 was dissolved in 9.7 g of acetic acid to make solution A. Then 14.2 g of mesityl oxide, 24.7 g of acetic anhydride and 0.0 lg of Phenothiazine was charged in a flask and heated to 60 ° C . Solution A was added dropwise. The mixture was kept stirring at 60 ° ° C for 4 hrs. 31 P NMR showed 88.3% conversion of H 3 PO 3 and 86% selectivity for PoDM and its anhydride derivatives.
  • H 3 PO 3 was dried for about 4 hrs at 50 ° C under vacuum. lOg of dried H 3 PO 3 was dissolved in 12.35 g of acetic acid to make solution A. Then 14.2 g of mesityl oxide, 12.35 g of acetic anhydride and 0.01 g of phenothiazine was mixed together to make solution B. Next a three-necked flask was put in a oil bath at 60 ° C and then Solutions A and B were added dropwise and simultaneously over 70 min. After the addition, the mixture was kept stirring for another 4 hrs. 31 P NMR showed 97.5% conversion of H 3 P0 3 and 87% selectivity for PoDM and its anhydride derivatives.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP09850739A 2009-10-30 2009-10-30 Verfahren zur herstellung von konjugierten dienphosphonatverbindungen Withdrawn EP2493903A4 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2009/074726 WO2011050533A1 (en) 2009-10-30 2009-10-30 Method for preparing conjugated diene phosphonate compounds

Publications (2)

Publication Number Publication Date
EP2493903A1 true EP2493903A1 (de) 2012-09-05
EP2493903A4 EP2493903A4 (de) 2013-03-27

Family

ID=43921260

Family Applications (1)

Application Number Title Priority Date Filing Date
EP09850739A Withdrawn EP2493903A4 (de) 2009-10-30 2009-10-30 Verfahren zur herstellung von konjugierten dienphosphonatverbindungen

Country Status (7)

Country Link
US (1) US8895775B2 (de)
EP (1) EP2493903A4 (de)
JP (1) JP5559341B2 (de)
KR (1) KR20120127398A (de)
CN (1) CN102596975A (de)
BR (1) BR112012009354A2 (de)
WO (1) WO2011050533A1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103097038B (zh) * 2010-07-21 2014-06-11 索尔维投资有限公司 用稳定的有机层涂覆无机基体的方法
FR2997405B1 (fr) * 2012-10-29 2015-11-13 Rhodia Operations Utilisation d'une silice precipitee contenant du titane et d'un agent de couplage specifique dans une composition d'elastomere(s)
CN110903318B (zh) * 2019-12-23 2023-02-28 西北民族大学 一种烯基膦酸酯化合物的制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4507249A (en) * 1982-03-22 1985-03-26 Hoechst Aktiengesellschaft Process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2389576A (en) * 1943-08-16 1945-11-20 Monsanto Chemicals Esters of diolefinic phosphonic acids
US2486657A (en) * 1945-04-28 1949-11-01 Monsanto Chemicals Diolefin phosphonic acids and polymers thereof
US4170609A (en) 1973-08-20 1979-10-09 Turner William F Aldol condensation process
US4201669A (en) 1978-09-11 1980-05-06 Betz Laboratories, Inc. Deposit control through the use of oligomeric phosphonic acid derivatives
DE3033615A1 (de) * 1980-09-06 1982-09-30 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung von vinylphosphonsaeurederivaten und deren verwendung
JPS57104894A (en) * 1980-12-23 1982-06-30 Tokyo Shibaura Electric Co Test device for reactor circulation system
US4446046A (en) 1981-06-17 1984-05-01 Betz Laboratories, Inc. Poly (alkenyl) phosphonic acid and methods of use thereof
CA1183861A (en) * 1981-06-17 1985-03-12 Larry W. Becker Poly(alkenyl) phosphonic acid and methods of use thereof
US4526788A (en) 1983-03-18 1985-07-02 American Cyanamid Company Polymeric[[(oxazolidinyl)alkyl]amino]anthraquinones
JPS6133137A (ja) 1984-07-24 1986-02-17 Sumitomo Chem Co Ltd チグリルアルデヒドの製造方法
US5391816A (en) 1993-11-08 1995-02-21 Akzo Nobel N.V. Formation of 1-phenylvinyl-1-phosphonic acid
DE4416018A1 (de) 1994-05-06 1995-11-09 Hoechst Ag Verfahren zur Herstellung von Vinylphophonsäuren
US5783730A (en) * 1997-05-02 1998-07-21 Akzo Nobel Nv Formation of styrene phosphonic acid
WO2000078387A1 (en) 1999-06-22 2000-12-28 Blanco Ernesto E Safety trocar with progressive cutting tip guards and gas jet tissue deflector
EP1169996A1 (de) * 2000-07-06 2002-01-09 Ernst Mühlbauer Kg Phosphonsäuren enthaltendes Dentalmaterial
JP4207115B2 (ja) * 2002-12-26 2009-01-14 日産化学工業株式会社 リン系有機基含有高分子を含む反射防止膜形成組成物
US7442831B2 (en) * 2004-07-07 2008-10-28 Unichem Technologies, Inc. Methods of synthesizing phosphonic compounds and compounds thereof
CN101343289A (zh) * 2008-08-25 2009-01-14 苏州大学 一种合成有机膦酸酯衍生物的方法
WO2011050537A1 (en) * 2009-10-30 2011-05-05 Rhodia (China) Co., Ltd. Conjugated diene phosphinate compounds, preparation method and use thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4507249A (en) * 1982-03-22 1985-03-26 Hoechst Aktiengesellschaft Process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
KAMAL M ET AL: "Synthesis of Phosphonate Analogues of Retinyl Phosphate", BIOORGANIC & MEDICINAL CHEMISTRY LETTERS, PERGAMON, ELSEVIER SCIENCE, GB, vol. 5, no. 21, 2 November 1995 (1995-11-02), pages 2461-2464, XP004136806, ISSN: 0960-894X, DOI: 10.1016/0960-894X(95)00431-R *
PUDOVIK, M. A. ET AL.: "Reactions of dialkyl phosphites with unsaturated ketones", JOURNAL OF GENERAL CHEMISTRY OF THE U.S.S.R (ENGLISH), vol. 46, 1976, pages 1430-1435, XP008160160, ISSN: 0022-1279 *
See also references of WO2011050533A1 *

Also Published As

Publication number Publication date
EP2493903A4 (de) 2013-03-27
KR20120127398A (ko) 2012-11-21
JP5559341B2 (ja) 2014-07-23
CN102596975A (zh) 2012-07-18
BR112012009354A2 (pt) 2016-11-22
US20120202957A1 (en) 2012-08-09
JP2013509354A (ja) 2013-03-14
US8895775B2 (en) 2014-11-25
WO2011050533A1 (en) 2011-05-05

Similar Documents

Publication Publication Date Title
US8835674B2 (en) Conjugated diene phosphinate compounds, preparation method and use thereof
US9403854B2 (en) Cross-metathesis reaction of functionalized and substituted olefins using group 8 transition metal carbene complexes as metathesis catalysts
EP3538508B1 (de) Rutheniumkomplexe zur katalysierung von metathesereaktionen
US8895775B2 (en) Method for preparing conjugated diene phosphonate compounds
KR100535166B1 (ko) 중합 가능한 비아릴, 이의 제조방법 및 이의 용도
CN102596976B (zh) N-取代的丙烯酰胺、其制备方法和用途
US3035096A (en) Vinyl diphenylphosphine oxide and method of producing same
Gulyukina et al. Synthesis of biologically active 1-arylethylphosphonates
Bałczewski et al. Studies on the free radical carbon-carbon bond formation in the reaction of α-phosphoryl sulfides and selenides with alkenes
Grineva et al. Organometallic manganese compounds in organic synthesis
EP1810975B1 (de) Verfahren zur herstellung von phosphonaten mit alkoholischer hydroxygruppe
EP3286161B1 (de) Verfahren zur herstellung verbrückter biaromatischer liganden
WO2023054663A1 (ja) ビニルホスホン酸モノエステルの製造方法
CN105523916B (zh) 合成奈妥吡坦中间体杂质2-(3,5-双三氟甲基苯基)丙酸的方法
CN117700449A (zh) 一种4-(羟基甲基膦酰基)-2-羰基丁酸的制备方法
Mphahlele et al. Reaction of carbanions generated from allylic phosphonates with β-substituted cyclic enones
JP2003300991A (ja) ブタジエニルホスホン酸環状エステル及びその製造法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120525

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20130222

RIC1 Information provided on ipc code assigned before grant

Ipc: C07B 47/00 20060101ALI20130218BHEP

Ipc: C07F 9/38 20060101ALI20130218BHEP

Ipc: C07F 9/40 20060101AFI20130218BHEP

17Q First examination report despatched

Effective date: 20150414

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20151027